Refractory zirconia casting



Patented June 27, 1944 I lumrao STATES PATENT oar-ice 2,352,530

REFRACTORY zmcoma CASTING Gordon S. Fuicher, Chevy Chase, Md, and Theodore E. Field, Louisville, Ky., assignors to Corhart Refractories Com corporation of Delaware pany, Louisville, Ky, '11

No Drawing. Application October 11, 1939, Serial No. 299,036

7 Claims.

which is especiallytroublesome in borosilieate glasses where the difference is emphasized by the low coefiicientofexpansion of theglass itself and where on the other hand superior resistance to thermal, shock is being sought. It is the purpose of thisv invention to provide a which minimizes these effects- Harmful cord effects can be minimized in two ways, In the first wamif resistance to chemical attack can be increased,the amount of cord forming refractory dissolved into the'glass is decreased. The process of melting and casting alumina-silica refractories, instead of burningthem, disclosed b U.. 8. Patent #1,615,750 to refractory We have discovered that the relatively poor resistance to corrosion of 100%-zirkite is apparently associated with a very poor glassphase resulting from the high iron oxide an titania'..- On the other hand zircon ls. recrystallized from a melt only on prolonged high temperature annealing, and the, practical result of melting and casting zircon in the usual 'way is to produce the a crystalline oxide and a silica glass saturated with zirconia. .This glass is approximately 50% of the volume-of ,the casting and since it has a softening point below the usual commercial glass melting temperatures, the'cast'ings are easily deformed and rapidly dissolved. While zircon has been used as major constituent in burned refract'ories, a commercially economical and satisfactory bonding for use 'in'glass furnaces has] not been achieved. -Pure zirconia'has likewise: been'used as an ingredient for burnedrefractoriesand in this case also a commercially practicable bond satisfactory both from' the stand- Fulcher, tends to this end. In the'second way.

the strain produced by cord canbe minimized if a sumciently resistant composition which procan be found. We have discovered that certain compositions high in zirconia are satisfactory in this respect when melted and cast byth'e methods disclosed in U. S. #1,6l5,750.

The commercial sources of zirconia are a crude oxide sold as zirkite which contains considerable silica, iron oxide, and alumina, and, the silicate known as zircon which is relatively pure but has 35% SiOz. Typical'analyses of these are as follows:

Zirkitel Zircon Zircon 5. l6 l2 5. 36 01 84 30 1. 75 3i l0 00 i5 .05 .56 02 00 .68 l5 While cast refractories in which zirconia is substituted for part of the alumina were disclosed in U. S. Patent #1.615,751 to Fulcher, complete substitution is not feasible from the stand point of resistance and was notdisclosed therein.

duces a cord with low coefficient of expansion of their porosity which effectively increases the point-of chemical resistance and its ability, to" make the product non-porous has. not, been" achieved; Thus it appears that whlleboth zircon and pure zirconia have long been' recognized as 2 excellent refractories, available bonds have been;

either too-low in resistance toward glass or required too high burning temperatures to be commercially practicable and such refractories are inherently less resistant than desirable because with cake in: an electric furnace,which results conia is the most resistant: to fiuxing by glass,'-"*

in reduction and volatilization of most of the silicatogive a product about ZrOz and 5% S10 If the latter product is remelted without coke, the remaining silica is volatilizedyby the high temperature. attainedand a pig-of substantially pure fused'zirconiais obtained.

We have discoveredthat. with certain addi-- tions, we" can prepare castrefractories from these materials which are not only free from alumina and therefore .of its cord forming proclivities but arealso significantly more'resistant than earlier refractories so that a smaller amount is dissolved into the glass. While it can be demonstrated that zirits high melting point of 2700 C. makes its use difficult in practical manufacture.

We have dis- 7 covered however that various fiuxe can'be added in certain proportions withoutdecreasing the resistancebelow useful limits. The fluxes we prefer are alkalies, alkaline earths and silica since all. of these are normal 1 constituents: off commercial glasses and do not produce color or' gas by reaction; y I

We have'found that as much'as of K;

NazO. or LizO can be introduced, as a carbonate.

for example, into a pure zirconia cast refractory without lowering the resistance excessively) However, the volatility of the unreacted' alkali inthe batch is so high that a considerableexcess' must be used in the batch toobtaina', given :result, especially when the melt is; smallfandthis it obviously increases the cost unless means for recovering the condensed alkali areiemployed; For

example in one small batch, NazO (44 parts" dense NazCOa) had to be addedto give..18-% NazO inthe castings. The loss is naturally lower with the higher percentages of jfiux. we ,normally prefer to uselIazCO:v sincefiNaaO .ls the cheapest alkali and-this salt isv notes volatilea: some. A suitable. batch is the following-when and finer mesh ZrOz is. used.

Casting analysis Batch 1 analysis 80 parts ZrOi 15% Nazt).

but is' harder to cast; loss is greater.

and the percentage alkali.

o th'ejother hand magne voamizaaon,

temperature of theoxides of alkalinezearths viz.,. beryllium, magnesium, calcium, .str0ntium,. a!1d bariuml permits rather complete retention. in

the product when one or more of., these are.

used as fluxes for pure:zircon ia. ,Asmuchas.

25 fcan be added withoutv decreasing theresistance excessively. CaO, SrO, and BaO, form zirconates" when too much usedf-andvthese phases are definitely'jinierior toy baddeleyite in. BaO produces the greatest fluxing for its weight, and compositions with this oxide.v

resistance.

are therefore easiest tocast; The; alkaline earths. can "obviously ,be introduced in any formwhich.- yields the oxide bydissociation-at elevated.tem-.

peratures. With -BaO' for example one can. use? the'monoxide, dioxide carbonate, or. sulphate using" alkaline earths as. fluxes Casting 30 Lower alkali" will give somewhat more resistance "alkaline earth for a very resistantatr'e'f" conveniently. Weprefer a batch asfollows when as follows v 7 Batch I analysis analysisss artsz'roi..; 1 v 85% 2:01.. 85% 2:0,; 19 parts BaCQa; 15% 1150:. 15% BM). 7

Because ofthe extra melting operation required in manufacturing pure zirconia, it is significantly more expensive-than the material produced'from. the first furn'acing with ab0ut'5'% SiO: with the zirconia; Where the utmost resistance. is not required therefore we preferfor purposes of} economy to utilize this-crude oxide. Silica itself is a flux for zirconia and'we have found it' possible,- although. difllcult, to remelt' and cast'this crude oxide to produce avery-"resistantcasting consisting of course of. crystalline Z1102 (baddeleyite andasilic'a glasssaturated with -zirconiap. If the metal .is poured-as fast as accumulated, and the crownkept covered with fresh batch, not n uchsilica isavolatilized. As stated above, zircon with 35"; silica is poor because of too.

much silica glass phase. The very good crude oxide can however be mixed with zircon to give a cheaper composition easier to cast and intermediate in silica and in resistance. We have discovered that silica can increased to 20% resistance is decrea's excessively. The effect of increasing the silica with the usual cast- .ing practice is to increase the amount of silica "glass saturated with zirconia, rather than to re- 10 crystalli'ie z'ircofn. As desirable batches, we may cite tn containing somesilica, and we prefer to com 40..

-. I v: 1 ,21. A

Among'the alkaline earths, BaO is the most powerful flux and 5% is quite suflicient to permit A. greater fluxing action with smaller}; t amounts of flux and'therefore with a-larg er centage of the resistant crystalline zroz pha can be obtained by using two 'fiuxes" toge'th From the standpoint of cost it is advantage I tov useas raw material the crude zirconiumo binethis withalkalies or alkaline earths.- Irr tfiis case we-obtain analkali-silic'a. or alkaline as silica glass phasefsaturated' with zirconi matrix for-the crystallinezirconia. Fromt standpoint of resistance to, corrosion 'th pr portions-can naturally be-varied from=20 Bibi, to 15%.alkali to 25% alkaline earth a above for the individual limits. wefipr'efnhow-x ever to aimat 5% SiOrandl to 12% snails Whenalkali is to be used it maybe adv to'use the oxide prepared. chemically from zircon since the residual alkali- -pr not. easily volatilize. Satisfactory b'at'c es ready casting of the crud zirconia. Satisfactory I batches are the following:

With more silica, less other flux is required for the same ease of melting, or if the additional fluxes are held constant and silica increased, the ease of casting is increased but the resistance to attack is decreased. The most economical batch obviously depends upon the degree of resistance required and the tolerance permissible for dis-- solved refractory.

In the following claims we use the term heat cast" to identify a refractory which forms on the solidification of molten material, thereby distinguishing it from a wet cast product.

What we claim is:

1. A heat cast refractory for contact with molten glass consisting essentially of zirconia and at least one of the alkalies L120, NazO and K20 in which the total alkali is less than 15% by weight by chemical analysis, and substantially free from alumina.

2. A heat cast refractory for contact with molten glass consisting essentially of zirconia and silica in which the silica is less than 20% by weight by chemical analysis, and substantially free from alumina.

3. A heat cast refractory fo'r contact with molten glass consisting essentially of zirconiaf silica and at least one of the allcalies LizO, NazO and K20 in which the silica is not more than 20% nor the total alkalies more than 15% by weight by chemical analysis and which is substantially free from alumina. I

4. A heat cast refractory for contact with molten glass consisting essentially of zirconia, silica and at least one of the alkaline earth oxides BeO, MgO, CaO, SrR and BaO in which the silica is not more than 20% nor the total alkaline earths more than 25% by weight by chemical analysis and which is substantially free from alumina.

5. A heat cast refractory for contact with molten glass consisting essentially of zirconia and silica in which the silica is less than 5% by weight by chemical analysis, and substantially free from alumina.

6. A heat cast refractory for contact with molten glass consisting essentially of zirconia, silica and at least one of the alkalies Li2O, M120 and K20 in which the silica is not more than 5% nor the total alkalies more than 15% by weight by chemical analysis and which is substantially free from alumina.

7. A heat cast refractory for contact with molten glass consisting" essentially of zirconia, silica and at least one of the alkaline earth oxides BeO, MgO, CaO, SrO and BaO in which the silica is not more than.5% nor the total alkaline earths less than 5% or more than 25% by weight by chemical analysis and which is substantially free from alumina.

GORDON S. FULCHER. THEODORE E. FIELD. 

